EP1043790A1 - Current collector coating of lithium storage batteries - Google Patents
Current collector coating of lithium storage batteries Download PDFInfo
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- EP1043790A1 EP1043790A1 EP00420069A EP00420069A EP1043790A1 EP 1043790 A1 EP1043790 A1 EP 1043790A1 EP 00420069 A EP00420069 A EP 00420069A EP 00420069 A EP00420069 A EP 00420069A EP 1043790 A1 EP1043790 A1 EP 1043790A1
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- electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/10—Battery-grid making
Definitions
- the present invention relates to an applied current protective coating on the metal collector of an electrode.
- the protective coating includes a binder partially or completely vitreous mineral and optionally a conduction additive electronic. This coating is applied as a solution or dispersion on the electrode collector, and dried, so as to cover and protect at least part of the metal surface of the collector to avoid the formation of insulating films generated by the active species from the other components of the generator.
- Lithium batteries in principle offer the unique advantage of achieving unsurpassed volume and specific energies that make them particularly interesting for a wide range of stationary or mobile applications ranging from microelectronics, from portable electronics to large installations for electric or hybrid electric vehicles.
- liquid aprotic electrolytes mainly lithium-ion type and more recently polymer electrolytes, these the latter being either of the dry solvating polymer type, operating between 40 and 100 ° C. with lithium anodes, either of gelled type, using a solvating polymer or not, and operating at room temperature by adding aprotic liquid solvents polar in combination with lithium-ion type electrodes including cathodes operate at high voltages ( ⁇ 4V). Extreme temperature or high operating voltages specific to these systems tend to age the different components of the generator during cycling and / or as a function of time.
- the aging of the components is reflected in particular in terms of current collectors and causes the formation of passivation or degradation films on the surface of these by reaction with the components of the generator, in the occurrence of the active materials of the electrodes and the chemical components of the organic electrolyte.
- the formation of such more or less insulating films at the interfaces greatly alters the quality of electronic exchanges between collectors and active electrode materials, which are usually present as composites.
- a long known way to protect metal collectors from current of electrochemical accumulators of passivation / dissolution phenomena is to cover these with an electronically conductive carbon coating oxidizable.
- dispersions of carbon blacks in organic binders or minerals are used in the form of a more or less waterproof base layer the electrolyte of the generator so as to avoid corrosion phenomena electrochemical.
- these coatings avoid direct contact of the collector with the active materials of the electrode (see for example US Pat. No. 5,262,264).
- US Patent 5,580,686 (Fauteux et al.) Describes a protective coating (“primer”) based on carbon dispersed in a metallic polysilicate used in a lithium-ion type electrolytic cell comprising a cobalt oxide cathode and a graphite anode.
- Polysilicates have several limitations due to their high basicity. Thus, they are reactive towards active materials of acid electrodes such as vanadium oxide. In addition, they are chemically reactive with materials of the type iron phosphate. Their basic nature also makes them incompatible with additives conduction consisting of conjugated polymers of polyaniline, polypyrole type doped etc.
- carbon is the additive generally preferred to because of its high chemical inertness and its resistance to electrochemical corrosion.
- the present invention relates to an electrochemical generator comprising a electrolyte separator between two electrodes of which at least one of the electrodes uses a metallic current collector partially or completely covered with a coating protective conductor, chemically compatible with the adjacent electrode material, said coating comprising a vitreous or partially vitreous mineral binder in which is optionally dispersed an electronic conduction additive ensuring exchanges electronics between the electrode and the collector, said coating being brought into contact waterproof with said collector in order to protect the metal surface covered with the formation of passivation films generated by reactive species from generator components.
- an electrode comprising a metal current collector partially or completely covered with a coating protective conductor, chemically compatible with the adjacent electrode material, said coating comprising a vitreous or partially vitreous mineral binder in which is optionally dispersed an electronic conduction additive ensuring exchanges electronics between the electrode and the collector, said coating being brought into contact waterproof with said collector in order to protect the metal surface covered with the formation of passivation films generated by reactive species from generator components.
- Figures 1a) and 1b) illustrate a composite collector / electrode assembly and the localization of the passivation film at the collector / electrode interface after cycling.
- Figures 2a) and 2b) illustrate an electrochemical generator comprising a collector whose surface has been coated with a coating according to the present invention.
- Figures 3 and 4 illustrate the cycling results of the electrochemical generator described in Example 3 in the presence of a protective coating of collector based on (LiPO 3 ) n and carbon black ( Figure 3) and in the absence of such a coating ( Figure 4).
- a vitreous or partially mineral binder is used vitreous, based on phosphate, polyphosphate, borate, or metal polyborate alkalis such as lithium or potassium alone or in the form of mixtures, in which optionally dispersing at least one electronic conduction additive.
- the phosphate compounds represent a preferred implementation for wet and protect the metal collectors used in generators electrochemical.
- these compounds in solution in water make it possible to control the pH and avoid acid-base reactions between the mineral binder and additives or materials of electrodes during the implementation of the films and the use of the generator electrochemical.
- Glass-forming additives such as hydrolyzed silica, partially or fully hydrolyzed organometallic siloxanes, aluminates, titanates are included in the present invention as long as these remain chemically compatible with conduction additives and with the active materials of the electrode, that is to say as long as one can control their acid-base properties so as to avoid chemical reactions harmful to the operation of the generator.
- the training additive glass is preferably added in the form of an aqueous or alcoholic solution in the solution of the mineral binder before neutralization, which is preferably carried out at a pH varying between 4 and 9.
- Carbon blacks and graphite are the electronic conduction additives preferential and can be added in concentrations varying preferentially between 2 and 20% by volume. These additives are preferably added in dispersed form in the mineral binder in the pure state or mixed so as to induce a conductivity essential electronics for maintaining electron exchanges between the substrate metal and the active materials of the electrode.
- Non-carbon additives are particularly sought after in high power devices or the level of conductivity required is significantly higher than 1 S / cm.
- the important property sought for the mineral binder is its ability to wet and protect the metal surface of the current collector to prevent the access of the generator components to the surface of the latter, in this case the electrolyte, the active materials of the electrode etc.
- the protected area is not subject to corrosion / passivation reactions, and optionally comprising an additive of conduction, it is then enough to maintain a permanent electronic contact between the metal and the conductive components of the adjacent electrode.
- the thicknesses sought for the coatings of the present invention will be of the order of a few microns in order to minimize the weight or the dead volume of the covering relative to the active materials of the generator.
- the thickness of the generator is less than 10 micrometers, and more preferably less than 4 micrometers.
- An optional way of carrying out the invention aimed at optimizing the content energy consists in using all or part of an electronic conduction additive which is also an active material of the electrode, in which case we will use a material finely ground, i.e. smaller than a micrometer, to reduce the stress caused by the volume variations of the electrode material, and materials whose variations in volume during cycling are less than 10%, and preferably less than 5%. Even if the preferential rate of mineral binder must be between 15 and 95%, in this embodiment of the invention, the level of mineral binder will also be high as possible, preferably greater than 30%, in order to preserve the mechanical integrity and the role of glass binder despite discharge / charge cycles and variations in volume.
- a particularly preferred embodiment of the invention consists in using a lithium polyphosphate of general formula (LiPO 3 ) n , which can be prepared in aqueous solution from a solution of neutralized acid (HPO 3 ) n , preferably between pH 4 and 9, with a lithium salt such as Li 2 O, LiOH or Li 2 CO 3 .
- the electronic conduction additive is then dispersed in the solution and coated on the current collector.
- the collector coatings according to the present invention can be used on various types of current collector, in particular aluminum and metallizations aluminum of a few hundred angstroms. It is interesting to note that these the latter are normally incompatible with a basic mineral binder such as lithium polysilicates.
- a binder solution of the (LiPO 3 ) n type is neutralized at a pH close to 7 while a second solution is brought to pH 11.
- the two solutions are then brought into contact with a V 2 O 5 powder.
- the solution retains the orange color of V 2 O 5
- the second case there is the formation of a green solution resulting from 'a chemical reaction between the binder and the solid oxide.
- a similar observation is made when the same vanadium oxide is contacted with an aqueous solution of lithium polysilicate.
- An aqueous solution of acid (HPO 3 ) n is neutralized at a pH close to 7 with lithium hydroxide.
- Carbon black (Ketjenblack TM EC-600) is dispersed therein at a rate of 8% by volume, relative to the glass of formula (LiPO 3 ) n .
- the suspension is then coated on a 13 micron aluminum collector. The thickness obtained after drying at 150 ° C is approximately 3 micrometers. We can see the shiny and adhesive appearance of the protective coating as well as its electronic conductivity on the surface.
- An identical test using potassium hydroxide to neutralize the acid (HPO 3 ) n gives a sample whose coating is even more flexible and adhesive.
- the collector based on (LiPO 3 ) n of Example 2 is used for the production of an electrochemical generator according to the following steps.
- a composite cathode is coated on the protected collector based on (LiPO 3 ) n of Example 2 to form a thin film from a dispersion in acetonitrile of the following elements, namely a) a copolymer based on ethylene oxide (55% volume) containing the LiTFSI salt at a concentration corresponding to an O / Li molar ratio of 30; b) powder V 2 O 5 (40%), and c) carbon black (Ketjenblack TM, 5% volume). After coating, the film is dried at 80 ° C under vacuum for 12 hours.
- a complete cell is produced by successive assembly, by thermal transfer of the cathode films, of the separator of 20 micrometers also consisting of a copolymer of ethylene oxide and of LiTFSI, and of a metallic lithium anode.
- the reversible capacity of the battery is 5.03 C / cm 2 .
- Figure 3 illustrates the behavior of this cell as a function of cycling at 60 ° C.
- the UPS is around 100 ⁇ after around thirty cycles.
- Figure 4 illustrates an identical cell using however an aluminum collector not covered with the protective coating according to the present invention.
- the two cells are recharged at constant current in 6 hours in using an upper charging voltage limit of 3.1 V.
- 3.1 V an upper charging voltage limit
- a binder based on potassium polymetaphosphate (KPO 3 ) n obtained according to the procedure of Example 2 is used with a dispersion of carbon black (Ketjenblack TM) and iron phosphate whose particles are of submicron size.
- the mixed protective coating is approximately 4 microns thick. The visual appearance of this coating is somi-brilliant, qualitatively confirming the low porosity of the protective coating.
- the rate of glass used is 70% by volume relative to iron phosphate (20% by volume) and carbon black (10% by volume), in order to obtain a substantially dense and not very porous coating.
- a test of the electrochemical activity of this coating is carried out using this coating directly with a polymer electrolyte consisting of a copolymer of ethylene oxide and of LiTFSI and a metallic lithium anode in an assembly identical to that of the Example 3.
- a polymer electrolyte consisting of a copolymer of ethylene oxide and of LiTFSI and a metallic lithium anode in an assembly identical to that of the Example 3.
- a low and stable UPS value as a function of the discharge / charge cycles is also observed.
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Abstract
Description
La présente invention concerne un revêtement protecteur de courant appliqué sur le collecteur métallique d'une électrode. Le revêtement protecteur comprend un liant minéral partiellement ou totalement vitreux et optionnellement un additif de conduction électronique. Ce revêtement est appliqué sous forme de solution ou dispersion sur le collecteur de l'électrode, et séché, de façon à couvrir et protéger au moins une partie de la surface du métal du collecteur afin d'éviter la formation de films isolants engendrés par les espèces actives provenant des autres composantes du générateur.The present invention relates to an applied current protective coating on the metal collector of an electrode. The protective coating includes a binder partially or completely vitreous mineral and optionally a conduction additive electronic. This coating is applied as a solution or dispersion on the electrode collector, and dried, so as to cover and protect at least part of the metal surface of the collector to avoid the formation of insulating films generated by the active species from the other components of the generator.
Les accumulateurs au lithium offrent en principe l'avantage unique d'atteindre des énergies volumiques et spécifiques insurpassées qui les rendent particulièrement intéressants pour une vaste gamme d'applications stationnaires ou mobiles qui vont de la microélectronique, de l'électronique portable jusqu'aux larges installations pour les véhicules électriques ou hybrides électriques.Lithium batteries in principle offer the unique advantage of achieving unsurpassed volume and specific energies that make them particularly interesting for a wide range of stationary or mobile applications ranging from microelectronics, from portable electronics to large installations for electric or hybrid electric vehicles.
Ces systèmes utilisent généralement des électrolytes aprotiques liquides principalement de type lithium-ion et plus récemment des électrolytes polymères, ces derniers étant soit de type polymère solvatant sec, fonctionnant entre 40 et 100°C avec des anodes de lithium, soit de type gélifié, utilisant un polymère solvatant ou non, et fonctionnant à la température ambiante grâce à l'addition de solvants liquides aprotiques polaires en association avec des électrodes de type lithium-ion dont les cathodes fonctionnent à des tensions élevées (∼ 4V). Les conditions extrêmes de température ou de tension de fonctionnement élevées propres à ces systèmes ont tendance à faire vieillir les différentes composantes du générateur au cyclage et/ou en fonction du temps.These systems generally use liquid aprotic electrolytes mainly lithium-ion type and more recently polymer electrolytes, these the latter being either of the dry solvating polymer type, operating between 40 and 100 ° C. with lithium anodes, either of gelled type, using a solvating polymer or not, and operating at room temperature by adding aprotic liquid solvents polar in combination with lithium-ion type electrodes including cathodes operate at high voltages (∼ 4V). Extreme temperature or high operating voltages specific to these systems tend to age the different components of the generator during cycling and / or as a function of time.
Le vieillissement des composantes se traduit notamment au niveau des collecteurs de courant et entraíne la formation de films de passivation ou de dégradation en surface de ces derniers par réaction avec les composantes du générateur, en l'occurrence les matériaux actifs des électrodes et les composantes chimiques de l'électrolyte organique. La formation de tels films plus ou moins isolants aux interfaces altère grandement la qualité des échanges électroniques entre les collecteurs et les matériaux actifs d'électrode, qui sont généralement présents sous forme de composites.The aging of the components is reflected in particular in terms of current collectors and causes the formation of passivation or degradation films on the surface of these by reaction with the components of the generator, in the occurrence of the active materials of the electrodes and the chemical components of the organic electrolyte. The formation of such more or less insulating films at the interfaces greatly alters the quality of electronic exchanges between collectors and active electrode materials, which are usually present as composites.
En milieu électrolyte polymère, l'effet des phénomènes de passivation est parfois amplifié parce qu'à l'état solide, les produits formés par les réactions du solvant organique, du sel de lithium, des matériaux d'électrodes ou en provenance d'autres composantes du générateur tendent à s'accumuler à l'interface par manque de convection du solvant ou de solubilisation des films formés, ou encore par manque de réaction de corrosion/dissolution du métal et de renouvellement de la surface d'échange. L'attaque des collecteurs ou la formation de films de passivation en surface par oxydation/dissolution du conducteur métallique est généralement causée par des réactions électrochimiques, notamment d'oxydation ou réduction, initiées par des radicaux, des réactions acide-base ou encore des réactions chimiques d'oxydation-réduction plus ou moins catalysées par les matériaux en présence. Les Figures 1a) et 1b) illustrent un ensemble collecteur/électrode composite et la localisation du film de passivation à l'interface collecteur/électrode après cyclage.In a polymer electrolyte medium, the effect of passivation phenomena is sometimes amplified because in the solid state, the products formed by the reactions of the solvent organic, lithium salt, electrode materials or from other generator components tend to accumulate at the interface due to lack of convection solvent or solubilization of the films formed, or else by lack of reaction of corrosion / dissolution of the metal and renewal of the exchange surface. The attack collectors or the formation of passivation films on the surface by oxidation / dissolution of the metallic conductor is usually caused by reactions electrochemicals, in particular oxidation or reduction, initiated by radicals, acid-base reactions or chemical oxidation-reduction reactions more or less catalyzed by the materials present. Figures 1a) and 1b) illustrate a collector / composite electrode assembly and the location of the passivation film at the collector / electrode interface after cycling.
Les phénomènes de passivation sont particulièrement évidents dans le cas des collecteurs d'aluminium fréquemment utilisés pour leur bas coût et pour leurs propriétés de conduction thermique et électrique avec les cathodes associées à des voltages de fin de charge fréquemment supérieures à 3 et même à 4 volts.Passivation phenomena are particularly evident in the case of aluminum collectors frequently used for their low cost and for their properties of thermal and electrical conduction with the cathodes associated with voltages at the end of frequently charges more than 3 and even 4 volts.
Dans les systèmes de type lithium-ion utilisant des électrolytes liquides ou des polymères gélifiés avec des liquides, la corrosion de l'aluminium du collecteur de la cathode est généralement évitée par l'usage d'un sel ou d'un additif fluoré de type LiBF4 et LiPF6 qui forment facilement un film fluoré en surface de l'aluminium, ou encore par l'anion oxydant ClO4, évitant ainsi la corrosion profonde ou la dissolution du collecteur d'aluminium. Avec d'autres sels fluorés particulièrement stables, tels que le TFSI de formule (CF3SO2)2NLi la corrosion de l'aluminium au-dessus de 4 volts peut conduire à la désintégration complète du collecteur.In lithium-ion type systems using liquid electrolytes or gelled polymers with liquids, corrosion of the aluminum of the cathode collector is generally avoided by the use of a salt or a fluorinated additive of the type LiBF 4 and LiPF 6 which easily form a fluorinated film on the surface of aluminum, or also by the oxidizing anion ClO 4 , thus avoiding deep corrosion or dissolution of the aluminum collector. With other particularly stable fluorinated salts, such as the TFSI of formula (CF 3 SO 2 ) 2 NLi corrosion of aluminum above 4 volts can lead to complete disintegration of the collector.
En milieu polymère sec, la formation de films de passivation sur le collecteur d'aluminium d'une cathode à base d'oxyde de vanadium tel que V2O5, ne conduit pas à la dissolution du collecteur, mais plutôt à la formation de films de passivation plus ou moins isolants qui augmentent la résistance électrique entre le collecteur et la cathode composite. On constate alors la formation de films d'oxydation de l'aluminium à base d'oxygène et de fluor, visibles en microscopie électronique, qui atteignent des épaisseurs supérieures aux films d'alumine initialement présents en surface de l'aluminium. De tels films sont plus ou moins isolants électriques et nuisent donc au passage des électrons entre le collecteur et les matériaux actifs et de conduction électronique présents dans la cathode.In a dry polymer medium, the formation of passivation films on the aluminum collector of a cathode based on vanadium oxide such as V 2 O 5 , does not lead to the dissolution of the collector, but rather to the formation of more or less insulating passivation films which increase the electrical resistance between the collector and the composite cathode. We then observe the formation of aluminum oxidation films based on oxygen and fluorine, visible by electron microscopy, which reach thicknesses greater than the alumina films initially present on the surface of the aluminum. Such films are more or less electrically insulating and therefore hinder the passage of electrons between the collector and the active and electronically conducting materials present in the cathode.
Une façon connue depuis longtemps de protéger les collecteurs métalliques de courant des accumulateurs électrochimiques des phénomènes de passivation/dissolution est de recouvrir ces derniers d'un revêtement carboné conducteur électronique peu oxydable. Généralement, des dispersions de noirs de carbone dans des liants organiques ou minéraux sont utilisées sous forme de couche de fond plus ou moins étanches à l'électrolyte du générateur de façon à éviter les phénomènes de corrosion électrochimiques. De plus, ces revêtements évitent un contact direct du collecteur avec les matériaux actifs de l'électrode (voir par exemple le brevet US 5,262,264). Ces solutions sont utilisées avec succès dans plusieurs applications commerciales. Toutefois, aucune d'entre elles n'est parfaitement satisfaisante, particulièrement lorsque les générateurs électrochimiques sont utilisés dans les conditions extrêmes précédemment décrites et sur de longues périodes de temps, notamment à cause du manque d'imperméabilité et de stabilité chimique ou électrochimique des liants organiques, ou encore des additifs de conduction métalliques ou polymères conjugués.A long known way to protect metal collectors from current of electrochemical accumulators of passivation / dissolution phenomena is to cover these with an electronically conductive carbon coating oxidizable. Generally, dispersions of carbon blacks in organic binders or minerals are used in the form of a more or less waterproof base layer the electrolyte of the generator so as to avoid corrosion phenomena electrochemical. In addition, these coatings avoid direct contact of the collector with the active materials of the electrode (see for example US Pat. No. 5,262,264). These solutions are successfully used in several commercial applications. However, none of them is perfectly satisfactory, particularly when electrochemical generators are used in extreme conditions previously described and over long periods of time, notably because of the lack impermeability and chemical or electrochemical stability of organic binders, or still metallic conduction additives or conjugated polymers.
Le brevet US 5,580,686 (Fauteux et al.) décrit un revêtement protecteur ("primer") à base de carbone dispersé dans un polysilicate métallique utilisé dans une cellule électrolytique de type lithium-ion comportant une cathode d'oxyde de cobalt et une anode de graphite. Les polysilicates comportent plusieurs limitations à cause de leur forte basicité. Ainsi, ils sont réactifs vis-à-vis de matériaux actifs d'électrodes acides tel que l'oxyde de vanadium. De plus, ils sont réactifs chimiquement avec des matériaux de type phosphate de fer. Leur caractère basique les rend en outre incompatibles avec les additifs de conduction constitués de polymères conjugués de type polyaniline, polypyrole dopés etc.US Patent 5,580,686 (Fauteux et al.) Describes a protective coating ("primer") based on carbon dispersed in a metallic polysilicate used in a lithium-ion type electrolytic cell comprising a cobalt oxide cathode and a graphite anode. Polysilicates have several limitations due to their high basicity. Thus, they are reactive towards active materials of acid electrodes such as vanadium oxide. In addition, they are chemically reactive with materials of the type iron phosphate. Their basic nature also makes them incompatible with additives conduction consisting of conjugated polymers of polyaniline, polypyrole type doped etc.
Dans la plupart ces applications le carbone est l'additif généralement préféré à cause de sa grande inertie chimique et de sa résistance à la corrosion électrochimique.In most of these applications carbon is the additive generally preferred to because of its high chemical inertness and its resistance to electrochemical corrosion.
La présente invention concerne générateur électrochimique comprenant un électrolyte séparateur entre deux électrodes dont au moins une des électrodes utilise un collecteur de courant métallique partiellement ou totalement recouvert d'un revêtement conducteur protecteur, chimiquement compatible avec le matériau d'électrode adjacent, ledit revêtement comprenant un liant minéral vitreux ou partiellement vitreux dans lequel est optionnellement dispersé un additif de conduction électronique assurant les échanges électroniques entre l'électrode et le collecteur, ledit revêtement étant mis en contact étanche avec ledit collecteur afin de protéger la surface métallique couverte de la formation de films de passivation engendrés par les espèces réactives provenant des composantes du générateur.The present invention relates to an electrochemical generator comprising a electrolyte separator between two electrodes of which at least one of the electrodes uses a metallic current collector partially or completely covered with a coating protective conductor, chemically compatible with the adjacent electrode material, said coating comprising a vitreous or partially vitreous mineral binder in which is optionally dispersed an electronic conduction additive ensuring exchanges electronics between the electrode and the collector, said coating being brought into contact waterproof with said collector in order to protect the metal surface covered with the formation of passivation films generated by reactive species from generator components.
Dans un second aspect de l'invention, on retrouve un procédé de revêtement
partiel ou total d'un protecteur de courant sur le collecteur métallique d'une électrode, le
procédé comprenant:
Dans un troisième aspect de l'invention, on retrouve une électrode comprenant un collecteur de courant métallique partiellement ou totalement recouvert d'un revêtement conducteur protecteur, chimiquement compatible avec le matériau d'électrode adjacent, ledit revêtement comprenant un liant minéral vitreux ou partiellement vitreux dans lequel est optionnellement dispersé un additif de conduction électronique assurant les échanges électroniques entre l'électrode et le collecteur, ledit revêtement étant mis en contact étanche avec ledit collecteur afin de protéger la surface métallique couverte de la formation de films de passivation engendrés par les espèces réactives provenant des composantes du générateur.In a third aspect of the invention, there is an electrode comprising a metal current collector partially or completely covered with a coating protective conductor, chemically compatible with the adjacent electrode material, said coating comprising a vitreous or partially vitreous mineral binder in which is optionally dispersed an electronic conduction additive ensuring exchanges electronics between the electrode and the collector, said coating being brought into contact waterproof with said collector in order to protect the metal surface covered with the formation of passivation films generated by reactive species from generator components.
Les Figures 1a) et 1b) illustrent un ensemble collecteur/électrode composite et la localisation du film de passivation à l'interface collecteur/électrode après cyclage.Figures 1a) and 1b) illustrate a composite collector / electrode assembly and the localization of the passivation film at the collector / electrode interface after cycling.
Les Figures 2a) et 2b) illustrent un générateur électrochimique comprenant un collecteur dont la surface a été enduite d'un revêtement selon la présente invention.Figures 2a) and 2b) illustrate an electrochemical generator comprising a collector whose surface has been coated with a coating according to the present invention.
Les Figures 3 et 4 illustrent les résultats de cyclage du générateur électrochimique décrit dans l'exemple 3 en présence d'un revêtement protecteur de collecteur à base de (LiPO3)n et de noir de carbone (Figure 3) et en l'absence d'un tel revêtement (Figure 4).Figures 3 and 4 illustrate the cycling results of the electrochemical generator described in Example 3 in the presence of a protective coating of collector based on (LiPO 3 ) n and carbon black (Figure 3) and in the absence of such a coating (Figure 4).
Selon la présente invention, on utilise un liant minéral vitreux ou partiellement vitreux, à base de phosphate, de polyphosphate, de borate, ou de polyborate de métaux alcalins tels que le lithium ou le potassium seuls ou sous forme de mélanges, dans lequel on disperse optionnellement au moins un additif de conduction électronique. Les composés à base de phosphates représentent une mise en oeuvre préférentielle pour mouiller et ainsi protéger des collecteurs métalliques utilisés dans les générateurs électrochimiques. De plus, ces composés en solution dans l'eau permettent de contrôler le pH et d'éviter les réactions acide-base entre le liant minéral et les additifs ou les matériaux d'électrodes lors de la mise en oeuvre des films et de l'utilisation du générateur électrochimique. Des additifs formateurs de verre tels que la silice hydrolysée, les siloxanes, aluminates, titanates organométalliques partiellement ou totalement hydrolysés sont inclus dans la présente invention en autant que ces derniers demeurent chimiquement compatibles avec les additifs de conduction et avec les matériaux actifs de l'électrode, c'est-à-dire en autant que l'on puisse contrôler leurs propriétés acide-base de façon à éviter des réactions chimiques nuisibles au fonctionnement du générateur. L'additif formateur de verre est préférablement ajouté sous forme de solution aqueuse ou alcoolique dans la solution du liant minéral avant la neutralisation, qui est préférablement réalisée à un pH variant entre 4 et 9. According to the present invention, a vitreous or partially mineral binder is used vitreous, based on phosphate, polyphosphate, borate, or metal polyborate alkalis such as lithium or potassium alone or in the form of mixtures, in which optionally dispersing at least one electronic conduction additive. The phosphate compounds represent a preferred implementation for wet and protect the metal collectors used in generators electrochemical. In addition, these compounds in solution in water make it possible to control the pH and avoid acid-base reactions between the mineral binder and additives or materials of electrodes during the implementation of the films and the use of the generator electrochemical. Glass-forming additives such as hydrolyzed silica, partially or fully hydrolyzed organometallic siloxanes, aluminates, titanates are included in the present invention as long as these remain chemically compatible with conduction additives and with the active materials of the electrode, that is to say as long as one can control their acid-base properties so as to avoid chemical reactions harmful to the operation of the generator. The training additive glass is preferably added in the form of an aqueous or alcoholic solution in the solution of the mineral binder before neutralization, which is preferably carried out at a pH varying between 4 and 9.
Différents additifs de conduction électronique sont possibles avec les liants de la présente invention. Parmi ceux-ci on retrouve les noirs de carbone, les graphites, les métaux tels que le cuivre et l'argent, les composés minéraux conducteurs métalliques de type carbures, nitrures, siliciures ou même chalcogénures métalliques ou encore les polymères conjugués dopés tels que les polyanilines, les polypyroles etc., et leurs mélanges. Les noirs de carbone et le graphite sont les additifs de conduction électronique préférentiels et peuvent être ajoutés dans des concentrations variant préférentiellement entre 2 et 20% en volume. Ces additifs sont préférablement ajoutés sous forme dispersée dans le liant minéral à l'état pur ou mélangé de façon à induire une conductivité électronique essentielle pour le maintien des échanges d'électrons entre le substrat métallique et les matériaux actifs de l'électrode. Les additifs non-carbonés sont particulièrement recherchés dans les dispositifs de forte puissance ou le niveau de conductivité requis est nettement supérieur à 1 S/cm.Different electronic conduction additives are possible with the binders. the present invention. Among these are carbon blacks, graphites, metals such as copper and silver, the metallic conductive mineral compounds of like carbides, nitrides, silicides or even metallic chalcogenides or doped conjugated polymers such as polyanilines, polypyroles etc., and their mixtures. Carbon blacks and graphite are the electronic conduction additives preferential and can be added in concentrations varying preferentially between 2 and 20% by volume. These additives are preferably added in dispersed form in the mineral binder in the pure state or mixed so as to induce a conductivity essential electronics for maintaining electron exchanges between the substrate metal and the active materials of the electrode. Non-carbon additives are particularly sought after in high power devices or the level of conductivity required is significantly higher than 1 S / cm.
La propriété importante recherchée pour le liant minéral est sa capacité de mouiller et protéger la surface métallique du collecteur de courant, de façon à empêcher l'accès des composantes du générateur à la surface de ce dernier, en l'occurrence l'électrolyte, les matériaux actifs de l'électrode etc. La zone protégée n'étant pas soumise à des réactions de corrosion/passivation, et comportant optionnellement un additif de conduction, elle suffit alors à maintenir un contact électronique permanent entre le métal contacté et les composantes conductrices de l'électrode adjacente.The important property sought for the mineral binder is its ability to wet and protect the metal surface of the current collector to prevent the access of the generator components to the surface of the latter, in this case the electrolyte, the active materials of the electrode etc. The protected area is not subject to corrosion / passivation reactions, and optionally comprising an additive of conduction, it is then enough to maintain a permanent electronic contact between the metal and the conductive components of the adjacent electrode.
En milieu polymère sec notamment, où la dissolution complète du collecteur n'est pas observée, il n'est pas nécessaire de recouvrir la totalité de la surface du métal de collection, en autant que seule la surface non-recouverte sera éventuellement passivée sans empêcher les échanges électroniques au niveau des surfaces protégées. Cette caractéristique de l'invention permet ainsi d'optimiser le taux de liant minéral requis de façon à laisser une porosité résiduelle suffisante pour permettre au moins un ancrage superficiel de l'électrode composite sur le revêtement conducteur de protection.In dry polymer medium in particular, where the complete dissolution of the collector is not observed, it is not necessary to cover the entire surface of the metal with collection, as long as only the uncovered surface will eventually be passivated without preventing electronic exchanges on protected surfaces. This characteristic of the invention thus makes it possible to optimize the rate of mineral binder required to so as to leave sufficient residual porosity to allow at least one anchoring surface of the composite electrode on the conductive protective coating.
Les épaisseurs recherchées pour les revêtements de la présente invention seront de l'ordre de quelques microns afin de minimiser le poids ou le volume mort du recouvrement relativement aux matériaux actifs du générateur. Préférentiellement, l'épaisseur du générateur est inférieure à 10 micromètres, et plus préférentiellement inférieure à 4 micromètres.The thicknesses sought for the coatings of the present invention will be of the order of a few microns in order to minimize the weight or the dead volume of the covering relative to the active materials of the generator. Preferably, the thickness of the generator is less than 10 micrometers, and more preferably less than 4 micrometers.
Une façon optionnelle de réaliser l'invention visant à optimiser le contenu énergétique consiste à utiliser en tout ou en partie un additif de conduction électronique qui est également un matériau actif de l'électrode, auquel cas on utilisera un matériau finement broyé, i.e. de taille inférieure au micromètre, pour réduire le stress engendré par les variations volumiques du matériau d'électrode, et on sélectionnera des matériaux dont les variations de volume au cyclage sont inférieures à 10%, et préférentiellement inférieures à 5%. Même si le taux préférentiel de liant minéral doit se situer entre 15 et 95%, dans ce mode de réalisation de l'invention, le taux de liant minéral sera aussi élevé que possible, préférentiellement supérieur à 30%, afin de préserver l'intégrité mécanique et le rôle de liant du verre en dépit des cycles de décharge/charge et des variations de volume. An optional way of carrying out the invention aimed at optimizing the content energy consists in using all or part of an electronic conduction additive which is also an active material of the electrode, in which case we will use a material finely ground, i.e. smaller than a micrometer, to reduce the stress caused by the volume variations of the electrode material, and materials whose variations in volume during cycling are less than 10%, and preferably less than 5%. Even if the preferential rate of mineral binder must be between 15 and 95%, in this embodiment of the invention, the level of mineral binder will also be high as possible, preferably greater than 30%, in order to preserve the mechanical integrity and the role of glass binder despite discharge / charge cycles and variations in volume.
Un mode de réalisation particulièrement préféré de l'invention consiste à utiliser un polyphosphate de lithium de formule générale (LiPO3)n, qui peut être préparé en solution aqueuse à partir d'une solution de l'acide (HPO3)n neutralisée, préférentiellement entre les pH 4 et 9, avec un sel de lithium tel que Li2O, LiOH ou Li2CO3. L'additif de conduction électronique est alors dispersé dans la solution et enduit sur le collecteur de courant.A particularly preferred embodiment of the invention consists in using a lithium polyphosphate of general formula (LiPO 3 ) n , which can be prepared in aqueous solution from a solution of neutralized acid (HPO 3 ) n , preferably between pH 4 and 9, with a lithium salt such as Li 2 O, LiOH or Li 2 CO 3 . The electronic conduction additive is then dispersed in the solution and coated on the current collector.
Les revêtements de collecteur selon la présente invention peuvent être utilisés sur divers type de collecteur de courant, notamment de l'aluminium et des métallisations d'aluminium de quelques centaines d'angström. Il est intéressant de noter que ces dernières sont normalement incompatibles avec un liant minéral basique comme les polysilicates de lithium.The collector coatings according to the present invention can be used on various types of current collector, in particular aluminum and metallizations aluminum of a few hundred angstroms. It is interesting to note that these the latter are normally incompatible with a basic mineral binder such as lithium polysilicates.
Les exemples suivants sont fournis afin d'illustrer la présente invention, et ne doivent en aucun temps être considérés comme en limitant la portée.The following examples are provided to illustrate the present invention, and are not should at no time be considered as limiting the scope.
Une solution de liant de type (LiPO3)n est neutralisée à pH voisin de 7 alors
qu'une seconde solution est amenée à pH de 11. Les deux solutions sont alors mises en
contact avec une poudre de V2O5. Dans le premier cas, c'est-à-dire lorsque le pH est
voisin de 7, la solution conserve la couleur orangée du V2O5, alors que dans le second cas,
on constate la formation d'une solution verte résultant d'une réaction chimique entre le
liant et l'oxyde solide. Une observation similaire est faite lorsque le même oxyde de
vanadium est mis en contact avec une solution aqueuse de polysilicate de lithium. Ces
observations sont faites pour illustrer l'importance d'assurer la compatibilité chimique du
liant minéral de protection du collecteur avec les matériaux actifs de l'électrode afin
d'éviter une détérioration progressive des performances d'un générateur au cyclage.A binder solution of the (LiPO 3 ) n type is neutralized at a pH close to 7 while a second solution is brought to
Une solution aqueuse d'acide (HPO3)n est neutralisée à pH voisin de 7 par de l'hydroxyde de lithium. On y disperse du noir de carbone (Ketjenblack™ EC-600) au taux de 8 % en volume, par rapport au verre de formule (LiPO3)n. La suspension est ensuite enduite sur un collecteur d'aluminium de 13 micromètres. L'épaisseur obtenue après séchage à 150°C est d'environ 3 micromètres. On constate l'aspect luisant et adhésif du revêtement de protection ainsi que sa conductivité électronique en surface. Un essai identique utilisant l'hydroxyde de potassium pour neutraliser l'acide (HPO3)n donne un échantillon dont le revêtement est encore plus flexible et adhésif.An aqueous solution of acid (HPO 3 ) n is neutralized at a pH close to 7 with lithium hydroxide. Carbon black (Ketjenblack ™ EC-600) is dispersed therein at a rate of 8% by volume, relative to the glass of formula (LiPO 3 ) n . The suspension is then coated on a 13 micron aluminum collector. The thickness obtained after drying at 150 ° C is approximately 3 micrometers. We can see the shiny and adhesive appearance of the protective coating as well as its electronic conductivity on the surface. An identical test using potassium hydroxide to neutralize the acid (HPO 3 ) n gives a sample whose coating is even more flexible and adhesive.
On utilise le collecteur à base de (LiPO3)n de l'exemple 2 pour la réalisation d'un générateur électrochimique selon les étapes suivantes. Une cathode composite est enduite sur le collecteur protégé à base de (LiPO3)n de l'exemple 2 pour former un film mince à partir d'une dispersion dans l'acétonitrile des éléments suivants, soient a) un copolymère à base d'oxyde d'éthylène (55 % volume) contenant le sel LiTFSI à une concentration correspondant à un rapport molaire O/Li de 30; b) la poudre V2O5 (40 %), et c) le noir de carbone (Ketjenblack™, 5% volume). Après enduction, le film est séché à 80°C sous vide durant 12 heures. On réalise une cellule complète par assemblage successif, par transfert thermique des films de cathode, du séparateur de 20 micromètres également constitué d'un copolymère d'oxyde d'éthylène et de LiTFSI, et d'une anode de lithium métallique. La capacité réversible de la pile est de 5,03 C/cm2. La Figure 3 illustre le comportement de cette cellule en fonction du cyclage à 60°C. On constate le bon maintien de la capacité lors des cycles successifs, et principalement le maintien de la valeur de l'A.S.I. (Area Specific Impédance) qui traduit la somme des phénomènes de résistance ohmique, de transfert de charge et de diffusion, et permet ainsi de juger du maintien de la qualité des contacts électriques. Dans cet exemple, l'A.S.I. est d'environ 100 Ω après une trentaine de cycles.The collector based on (LiPO 3 ) n of Example 2 is used for the production of an electrochemical generator according to the following steps. A composite cathode is coated on the protected collector based on (LiPO 3 ) n of Example 2 to form a thin film from a dispersion in acetonitrile of the following elements, namely a) a copolymer based on ethylene oxide (55% volume) containing the LiTFSI salt at a concentration corresponding to an O / Li molar ratio of 30; b) powder V 2 O 5 (40%), and c) carbon black (Ketjenblack ™, 5% volume). After coating, the film is dried at 80 ° C under vacuum for 12 hours. A complete cell is produced by successive assembly, by thermal transfer of the cathode films, of the separator of 20 micrometers also consisting of a copolymer of ethylene oxide and of LiTFSI, and of a metallic lithium anode. The reversible capacity of the battery is 5.03 C / cm 2 . Figure 3 illustrates the behavior of this cell as a function of cycling at 60 ° C. We note the good maintenance of the capacity during successive cycles, and mainly the maintenance of the value of the UPS (Area Specific Impedance) which translates the sum of the phenomena of ohmic resistance, charge transfer and diffusion, and thus allows to judge the maintenance of the quality of the electrical contacts. In this example, the UPS is around 100 Ω after around thirty cycles.
Par opposition, on illustre à la Figure 4, une cellule identique utilisant cependant un collecteur d'aluminium non recouvert du revêtement protecteur selon la présente invention. Les deux cellules sont rechargées à courant constant en 6 heures en utilisant une limite de voltage supérieure de recharge de 3.1 V. On constate dans ce second cas, une perte initiale importante de la capacité et une valeur de l'A.S.I. élevée dès le départ du cyclage. Cette perte est près de quatre fois supérieure à celle de l'essai précédent, confirmant ainsi le rôle protecteur du revêtement faisant l'objet de la présente demande.In contrast, Figure 4 illustrates an identical cell using however an aluminum collector not covered with the protective coating according to the present invention. The two cells are recharged at constant current in 6 hours in using an upper charging voltage limit of 3.1 V. We see in this second case, a significant initial loss of capacity and a value of the A.S. high as soon the start of cycling. This loss is almost four times that of the test previous, thus confirming the protective role of the coating which is the subject of the present request.
Un liant à base de polymétaphosphate de potassium (KPO3)n obtenu selon la procédure de l'exemple 2 est utilisé avec une dispersion de noir de carbone (Ketjenblack™) et de phosphate de fer dont les particules sont de taille submicroniques. Le revêtement protecteur mixte est d'une épaisseur d'environ 4 micromètres. L'apparence visuelle de ce revêtement est somi-brillante, confirmant qualitativement le caractère peu poreux du revêtement protecteur. Le taux de verre utilisé est de 70 % en volume relativement au phosphate de fer (20 % en volume) et au noir de carbone (10 % en volume), afin d'obtenir un revêtement sensiblement dense et peu poreux. Un test de l'activité électrochimique de ce revêtement est effectué en utilisant ce revêtement directement avec un électrolyte polymère constitué d'un copolymère d'oxyde d'éthylène et de LiTFSI et une anode de lithium métallique dans un montage identique à celui de l'exemple 3. On constate alors une activité électrochimique propre à l'additif de phosphate de fer avec un plateau de décharge de 3.3 V et une capacité proportionnelle à la quantité d'additif. Une valeur d'A.S.I. faible et stable en fonction des cycles de décharge/charge est également observée.A binder based on potassium polymetaphosphate (KPO 3 ) n obtained according to the procedure of Example 2 is used with a dispersion of carbon black (Ketjenblack ™) and iron phosphate whose particles are of submicron size. The mixed protective coating is approximately 4 microns thick. The visual appearance of this coating is somi-brilliant, qualitatively confirming the low porosity of the protective coating. The rate of glass used is 70% by volume relative to iron phosphate (20% by volume) and carbon black (10% by volume), in order to obtain a substantially dense and not very porous coating. A test of the electrochemical activity of this coating is carried out using this coating directly with a polymer electrolyte consisting of a copolymer of ethylene oxide and of LiTFSI and a metallic lithium anode in an assembly identical to that of the Example 3. We then observe an electrochemical activity specific to the iron phosphate additive with a 3.3 V discharge plate and a capacity proportional to the quantity of additive. A low and stable UPS value as a function of the discharge / charge cycles is also observed.
Bien que la présente invention ait été décrite à l'aide de mises en oeuvre spécifiques, il est entendu que plusieurs variations et modifications peuvent se greffer aux dites mises en oeuvre, et la présente demande vise à couvrir de telles modifications, usages ou adaptations de la présente invention suivant, en général, les principes de l'invention et influant toute variation de la présente description qui deviendra connue ou conventionnelle dans le champ d'activité dans lequel se retrouve la présente invention, et qui peut s'appliquer aux éléments essentiels mentionnés ci-haut, en accord avec la portée des revendications suivantes.Although the present invention has been described using implementations specific, it is understood that several variations and modifications can be added to the said implementations, and the present request aims to cover such modifications, uses or adaptations of the present invention generally following the principles of the invention and influencing any variation of the present description which will become known or conventional in the field of activity in which the present invention is found, and which can apply to the essential elements mentioned above, in accordance with the scope of the following claims.
Claims (26)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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CA002268355A CA2268355A1 (en) | 1999-04-07 | 1999-04-07 | Lipo3-based collector coating |
CA2268355 | 1999-04-07 |
Publications (2)
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EP1043790A1 true EP1043790A1 (en) | 2000-10-11 |
EP1043790B1 EP1043790B1 (en) | 2005-08-03 |
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EP (1) | EP1043790B1 (en) |
JP (1) | JP2000340234A (en) |
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JP5914475B2 (en) | 2010-07-15 | 2016-05-11 | クラリアント (カナダ) インコーポレイテッド | Battery grade cathode coating formulation |
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EP1043795A2 (en) * | 1999-04-07 | 2000-10-11 | Hydro-Quebec | Electrochemical generator with composite electrode comprising two different solid electrolytes and process of manufacture |
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EP1043795A3 (en) * | 1999-04-07 | 2006-05-17 | Hydro-Quebec | Electrochemical generator with composite electrode comprising two different solid electrolytes and process of manufacture |
WO2015110715A1 (en) * | 2014-01-27 | 2015-07-30 | Hutchinson | Electrode for an electric-energy storage system with collector including a protective conductive layer and corresponding manufacturing method |
US10079118B2 (en) | 2014-01-27 | 2018-09-18 | Hutchinson | Electrode for an electric-energy storage system with collector including a protective conductive layer and corresponding manufacturing method |
Also Published As
Publication number | Publication date |
---|---|
US6844114B2 (en) | 2005-01-18 |
US6485866B1 (en) | 2002-11-26 |
EP1043790B1 (en) | 2005-08-03 |
CA2268355A1 (en) | 2000-10-07 |
DE60021643T2 (en) | 2006-05-24 |
JP2000340234A (en) | 2000-12-08 |
DE60021643D1 (en) | 2005-09-08 |
US20030022067A1 (en) | 2003-01-30 |
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